Perfluoroallyloxy compound and liquid crystal composition containing the same

ABSTRACT

A novel perfluoroallyloxy compound represented by general formula (I) and a liquid crystal composition containing the compound are disclosed. The perfluoroallyloxy compound is useful as a liquid crystal material

TECHNICAL FIELD

The present invention relates to a novel perfluoroallyloxy compound anda liquid crystal composition containing the same. The perfluoroallyloxycompound of the invention is useful as a liquid crystal material.

BACKGROUND ART

A large number of liquid crystal displays (LCDs) utilizing optical(refractive index) anisotropy (Δn) (hereinafter sometimes simplyreferred to as Δn) and dielectric anisotropy (Δε) (hereinafter sometimessimply referred to as Δε) characteristic of a liquid crystal compoundhave been produced. LCDs have been widely applied to watches,calculators, various measuring instruments, automotive panels, wordprocessors, electronic notebooks, mobile phones, printers, computers, TVsets, etc. with demand increasing year by year. A liquid crystalcompound exhibits an inherent liquid crystal phase between a solid phaseand a liquid phase. The liquid crystal phase is roughly classified intoa nematic phase, a smectic phase, and a cholesteric phase. For displayapplications, a nematic phase is most widely used. Number of displaymodes have been proposed for LCD application, including dynamic scatter(DS), guest host (GH), twist nematic (TN), super twist nematic (STN),thin film transistor (TFT), and ferroelectric liquid crystal (FLC).Drive systems known for LCD application include static drive, timedivision drive, active matrix drive, and dual frequency drive.

It is known that the threshold voltage of an electric field effect typeLCD using a liquid crystal composition having a positive dielectricanisotropy Δε is in general inversely proportional to the square root ofthe Δε. In recent years, a liquid crystal material with a decreasedthreshold value has been demanded particularly for application to twistnematic (TN) mode LCDs that have now mostly come to adopt a batterydrive system. To meet the demand, a liquid crystal material with a largepositive Δε is of importance.

Having a large Δε, nitrile compounds including a4-(p-alkylcyclohexyl)benzonitrile have been employed as a liquid crystalmaterial for TN mode LCDs or super twist nematic (STN) mode LCDs.However, because these nitrile compounds are liable to entrap ionicimpurities, they are inapplicable to active matrix drives requiring highresistivities (10¹² Ωcm or higher). Therefore, a liquid crystal materialwith high resistivity and large Δε has been awaited.

The viscosity of a liquid crystal composition influences the responsetime of LCDs. The lower the viscosity, the shorter the response time.Accordingly, it is desirable for the components compounded into a liquidcrystal compositions to have low viscosities.

The refractive index anisotropy exerts large influence on visualcharacteristics of LCDs. The contrast increases with an increase ofrefractive index anisotropy, and the viewing angle widens with adecrease of the anisotropy. In recent years there is a trend towardliquid crystal materials with a small Δn, namely a wide viewing angle.

An NI point governs the temperature range in which a liquid crystalmaterial shows a liquid crystal state. A liquid crystal material havinga higher NI point exhibits a liquid crystal state at a highertemperature.

Compounds terminated with a fluoroalkyl(oxy) group exhibit positivedielectric anisotropy and hardly entrap ionic impurities. They are knownas liquid crystal materials capable of developing characteristicsrequired particularly of active matrix drive systems, such as highresistivity, high voltage holding ratio (VHR), and a low ion density.Many compounds having a fluoroalkyl(oxy) group introduced therein havehitherto been proposed. For example, JP-A-55-72143, JP-A-55-40660,JP-A-61197563, JP-A-56-12322, JP-A-58-154532, JP-A-58-177939,JP-A-58-210045, JP-A-5978129, and JP-T-6-500343 propose various kinds offluoroalkyl-containing compounds. JP-T-1-503145 discloses anelectro-optical display device using a compound containing a fluoroalkylgroup. JP-T-3-502942 proposes an active matrix LCD using a compoundhaving a fluoroalkyl(oxy) group.

Nevertheless, the fluoroalkyl-containing compounds specificallydescribed in these publications are still unsatisfactory in terms of thedemand for low viscosity and a broader temperature range for a nematicphase.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a novel liquid crystalmaterial that can be mixed with a nematic liquid crystal material toprovide a liquid crystal composition having a low viscosity, a lowrefractive index anisotropy (Δn), a high dielectric anisotropy (Δε), anda high NI point (i.e., broad nematic phase range).

As a result of extensive investigations, the present inventors havefound that the above object of the invention is accomplished by aperfluoroallyloxy compound.

Based on the above finding, the present invention provides aperfluoroallyloxy compound represented by general formula (I) shownbelow and a liquid crystal composition containing the compound.

wherein R₁ represents R, RO, ROCO or RCOO; R represents an alkyl groupwhich may have an unsaturated bond, a —CH₂— moiety of which may bedisplaced with —O—, —CO— or —COO—, and a part or all of the hydrogenatoms of which may be substituted with a halogen atom or a cyano group;A₁ and A₂ each represent 1,4-phenylene (a —CH═ moiety of which may bedisplaced with —N═, and a part or all of the hydrogen atoms of which maybe substituted with a halogen atom or a cyano group), 1,4-cyclohexylene(a —CH₂— moiety of which may be displaced with —O— or —S—, and a part orall of the hydrogen atoms of which may be substituted with a halogenatom or a cyano group), 2,6-naphthylene or 2,6-decahydronaphthylene; Z₁represents a single bond, —COO—, —OCO—, —CH₂CH₂—, —CH═CH—, —(CH₂)₄—,—CH₂O—, —OCH₂—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CHCH₂O—, —OCH₂CH═CH—, —C≡C—,—CF₂O— or —OCF₂—; B represents a single bond or an alkylene group a partof the hydrogen atom of which may be substituted with a halogen atom ora cyano group; and n represents a number of 1 to 3; when n is 2 or 3,A₁'s and Z₁'s may each be the same or different.

BEST MODE FOR CARRYING OUT THE INVENTION

In general formula (I) representing the perfluoroallyloxy compound ofthe present invention, R₁ represents R, RO, ROCO or RCOO. The alkylgroup represented by R includes methyl, ethyl, propyl, butyl, pentyl,hexyl, heptyl, octyl, nonyl, decyl, vinyl, allyl, butenyl, ethynyl,propynyl, butynyl, methoxymethyl, ethoxymethyl, propoxymethyl,butoxymethyl, methoxyethyl, ethoxyethyl, perfluoromethyl,perfluoroethyl, perfluoropropyl, monofluoromethyl, difluoromethyl,2,2,2-trifluoromethyl, perfluorovinyl, perfluoroallyl, isopropyl,1-methylpropyl, 2-methylpropyl, 2-butylmethyl, 3-methylbutyl,2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-propylpentyl, and1-methylpentyl. R₁ is preferably an unsubstituted alkyl group, anunsubstituted alkenyl group or a group —O—CF₂CF═CF₂.

The following is a list of structures of the moiety —(A₁—Z₁)_(n)—A₂— ingeneral formula (I). Note that the perfluoroallyloxy compounds of theinvention are not limited by the list.

-   —CY—CY—-   —CY—PH—-   —PH—PH—-   —CY—PH3F—-   —CY—PH3,5—diF—-   —CY—PH2,3—diF—-   —CY—CY—CY—-   —CY—CY—PH—-   —CY—PH—PH—-   —PH—PH—PH—-   —CY—CY—PH3F—-   —CY—CY—PH3,5—diF—-   —CY—CY—PH2,3—diF—-   —CY—PH3F—PH—-   —CY—PH3,5—diF—PH—-   —CY—PH2,3—diF—PH—-   —CY—PH—PH—CY—-   —PH—CH₂CH₂—CY—CY—-   —CY—PH—CH₂CH₂—PH—-   —CY—CY—CH₂CH₂—PH—-   —CY—CH₂CH₂—CY—-   —PH—CH₂CH₂—CY—-   —PH—C≡C—PH—-   —CY—PH—C≡C—PH—-   —PH—COO—PH—-   —CY—COO—PH—-   —CY—CY—COO—PH—-   —PH—COO—PH—PH—-   -Pym-PH—-   -Dio-PH—-   —PH-Pym--   —PH-Dio--   —PH-Pyr--   —PH—CF₂O—PH—-   —PH—CH₂O—PH—-   —PH—CH═CHCH₂O—PH—-   —PH—(CH₂)₃O—PH—-   —CY—COO-Nap--   —CY—COO-DHN-

The abbreviations used in the above list stand for the following cyclicstructures.

In general formula (I), A₁ and A₂ each preferably represent anunsubstituted 1,4-phenylene group or an unsubstituted 1,4-cyclohexylenegroup, or at least one of A₁ and A₂ is preferably a 1,4-phenylene groupsubstituted with one or two fluorine atoms. Z₁ is preferably a singlebond or —CF₂O—.

The alkylene group represented by B in general formula (I) includesmethylene, ethylene, monofluoromethylene, monofluoroethylene,1,2-difluoroethylene, and 1,1,2-trifluoroethylene.

Specific examples of preferred perfluoroallyloxy compounds representedby general formula (I) include, but are not limited to, compound Nos. 1through 21 shown below. In compound Nos. 1 to 21, R₁ is as defined ingeneral formula (I).

Of the perfluoroallyloxy compounds of the present invention, thosecomposed of an unsubstituted benzene ring and/or an unsubstitutedcyclohexane ring (e.g., compound Nos. 1 to 4, 11, and 12) have a lowviscosity and a high NI point; and those having a benzene ringsubstituted with a fluorine atom at a lateral position thereof (e.g.,compound Nos. 13 to 21) are useful for their broad liquid crystal phaserange. In particular, those having a benzene ring substituted with afluorine atom at both the 2- and 3-positions (e.g., compound No. 21)have a negative Δε and are therefore useful as a material of verticalalignment type or guest-host type electro-optical devices. The othercompounds have various advantageous characteristics as well.

The process of producing the perfluoroallyloxy compound of the presentinvention is not particularly restricted. For example, the compound canbe prepared according to the following reaction scheme:

wherein R₁, A₁, A₂, Z₁, n, and B are as defined in general formula (I);X represents a halogen atom or FSO₂O—; BASE represents a base; and solv.represents a solvent.

The base that can be used in the reaction includes metal hydroxides,such as sodium hydroxide and potassium hydroxide; metal hydrides, suchas lithium hydride and sodium hydride; and amines, such astriethylamine, ethyldimethylamine, propyldimethylamine,N,N′-dimethylpiperazine, pyridine, picoline1,8-diazabicyclo(5.4.0)undecene-1 (DBU), benzyldimethylamine,2-(dimethylaminoethyl) phenol (DMP-10), and2,4,6-tris(dimethylaminomethyl)phenol (DMP-30).

In carrying out such etherification as represented by the reactionscheme shown above, Williamson's method is widely used, in which asodium alkoxide (or phenoxide) prepared from an alcohol compound (orphenol compound) and sodium hydroxide, etc. is allowed to react with analkyl halide. In the present invention, however, the desired compound ispreferably prepared by allowing a phenol compound and a halide orfluorosulfite of perfluoropropene to react in the presence of an aminecompound, especially a tertiary amine, such as triethylamine, whichachieves a high conversion. The reaction temperature and the reactiontime are selected appropriately from a range of −80° to 80° C. and arange of 0 to 20 hours, respectively.

The solvent that can be used in the reaction includes polar solvents,such as dimethylimidazoline, tetrahydrofuran, dimethylformamide, diethylether, and dimethylsulfone, and low polarity solvents, such as tolueneand ethyl acetate.

In the process according to the reaction scheme shown above, the hydroxycompound (1) and the perfluoro compound (2) are preferably used at a(1)/(2) mass ratio of 20/1 to 1/20, still preferably 1/1 to 1/10.

The base is preferably used in an amount of 0.1 to 5.0 equivalents,still preferably 1.0 to 2.0 equivalents, based on 1 equivalent of thehydroxy compound (1).

The amount of the solvent to be used preferably ranges, but is notlimited to, 10 to 500 parts by mass per 100 parts of the total of thehydroxy compound (1) and the perfluoro compound (2).

The perfluoroallyloxy compound of the present invention is compoundedwith a known liquid crystal compound or a liquid crystal-like compoundor a mixture thereof as a mother liquid crystal to provide a liquidcrystal composition according to the invention. The liquid crystalcomposition of the invention may consist of the perfluoroallyloxycompound(s) alone.

The mother liquid crystal includes compounds represented by generalformula (II) shown below and a mixture thereof.

wherein R represents a hydrogen atom, or such groups having 1 to 8carbon atoms as an alkyl group, an alkoxy group, an alkenyl group, analkenyloxy group, an alkynyl group, an alkynyloxy group, an alkoxyalkylgroup, an alkanoyloxy group and an alkoxycarbonyl group, wherein thosegroups may be substituted with a halogen atom, a cyano group, etc.; Y₂represents a cyano group, a halogen atom or a group represented by R;Y₁, Y₃, and Y₄ each represent a hydrogen atom, a halogen atom or a cyanogroup; Z₁ and Z₂ each represent a single bond, —CO—O—, —O—CO—, —CH₂O—,—OCH₂—, —CH₂CH₂—, —CH═CHCH₂O—, —CF₂O—, —OCF₂— or —C≡C—; p represents 0,1 or 2; ring D, ring E, and ring F each represent a benzene ring, acyclohexane ring, a cyclohexene ring, a pyrimidine ring or a dioxanering.

Specific examples of the compounds represented by general formula (II)are shown below. In the formulae, R, Y₁, Y₂, Y₃, and Y₄ are as definedin general formula (II).

The amount of the perfluoroallyloxy compound of the invention in theliquid crystal composition according to the invention is notparticularly limited and is selected appropriately so as to securedesired characteristics. For example, the amount is preferably selectedfrom the range 1 to 100% by mass, still preferably 5 to 90% by mass.

The liquid crystal composition containing the perfluoroallyloxy compoundof the present invention can be sealed in a liquid crystal cell toconstitute various types of electro-optical display devices. The liquidcrystal composition of the present invention is applicable to varioustypes of elector-optical display devices including dynamic scatter (DS)mode, guest-host (GH) mode, twist nematic (TN) mode, super twist nematic(STN) mode, thin film transistor (TFT) mode, thin film diode (TFD) mode,ferroelectric liquid crystal (FLC) mode, anti-ferroelectric liquidcrystal (AFLC) mode, is polymer dispersed liquid crystal (PDLC) mode,vertical alignment (VA) mode, and in-plane switching (IPS) mode. Thedrive systems to which the liquid crystal composition is applicableinclude static drive, time division drive, active matrix drive, and dualfrequency drive.

The perfluoroallyloxy compound of the invention can be combined with avariety of known liquid crystal materials to provide liquid crystalcompositions applicable to various electro-optical display devicesdifferent in kind of the alignment film or various characteristics suchas twist angle, tilt angle, dielectric anisotropy (Δε), resistivity,nematic phase range, viscosity, average dielectric constant, coefficientof viscosity, and voltage holding ratio.

With respect to electro-optical display devices and liquid crystalcompositions used therein, various proposals have been made, e.g., inJP-A-10-67989, JP-T-3-502942, JP-A-3-85532, JP-A-4-296387,JP-T-6-501517, JP-T-10-512914, JP-A-9-125063, JP-A-11-29771,JP-A-10-245559, JP-A-2000-351972, JP-A-2002-285157, JP-A-2002-302673,JP-T-2002-533526, JP-A-2002-114978, JP-T-5-501735, JP-A-2002-193853,JP-A-2002-193852, JP-T-5-500683, JP-A-2002-201474, JP-A-10-204016,JP-A-2000-73062, JP-A-2000-96056, JP-A-2001-31971, JP-A-2000-80371,JP-A-2001-354967, JP-A-2000-351972, WO 99/21815, WO 99-21816, WO97/36847, U.S. Pat. Nos. 5,456,860 and 5,578,241, EP 662,502, and GermanPatent 10117224. The perfluoroallyloxy compound of the present inventioncan be used in combination with these electro-optical display devices orliquid crystal compositions.

The electro-optical display devices using the perfluoroallyloxy compoundof the present invention are useful in applications including watches,calculators, measuring instruments, automotive instrumentation, copiers,cameras, office automation equipment, handheld personal computers, andmobile phones. They are also useful in other applications, such as smartwindows, optical shutters, and polarizing beam splitters.

The present invention will now be illustrated in greater detail withreference to Examples, but it should be understood that the invention isnot construed as being limited thereto.

EXAMPLE 1

Synthesis of Compound No. 1 (R₁: n-C₃H₇)

Compound No. 1(R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 1:

In a nitrogen stream, 1.2 g (4 mmol) of4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (1) was dissolved in 7 g ofdimethylimidazolidinone (DMI), and 1.03 g (4 mmol) of3-iodoperfluoropropene-1 (2) was added to the solution. To the mixturewas added 0.48 g (4.8 mmol) of triethylamine (TEA), followed by allowingthe mixture to react for 2 hours.

The reaction mixture was subjected to gas chromatography to determinethe reaction conversion from the area percentages of the chromatogram.The area percentage of the raw material (1) was 9%, and that of theproduct (3) was 91%.

The reaction mixture was neutralized by addition of ethyl acetate andhydrochloric acid, washed with water until neutrality was confirmed,dried over magnesium sulfate, and filtered. The filtrate was subjectedto solvent exchange with toluene, treated with silica, and concentratedunder reduced pressure. The concentrate was purified successively bykugel-rohr distillation and crystallization (first stage: ethylacetate/methanol=1/18; second stage: acetone) to give 0.8 g (yield; 47%)of the title compound (3) with 99.9% purity as white crystals.

The resulting compound (3) was identified to be compound No. 1 (R₁:n-C₃H₇) by infrared (IR) absorption spectrum and ¹H-NMR analyses. Theanalytical results obtained are shown below.

[IR] 2920 cm⁻¹, 2850 cm⁻¹, 1794 cm⁻¹, 1609 cm⁻¹, 1508 cm⁻¹, 1447 cm⁻¹,1389 cm⁻¹, 1319 cm⁻¹, 1223 cm⁻¹, and 1196 cm⁻¹

[¹H-NMR] 7.3–7.0 (m, 4H), 2.6–2.3 (m, 1H), 2.2–0.4 (m, 26H)

EXAMPLE 2

Synthesis of Compound No. 1 (R₁: n-C₃H₇)

Compound No. 1(R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 2:

In a nitrogen stream, 2.71 g (5.65 mmol) of sodium hydride and 30 ml oftetrahydrofuran (THF) were put into a reactor, and a solution of 13 g(43.5 mmol) of 4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (1) in 120ml of tetrahydrofuran (THF) was added dropwise. After the mixture wasstirred for 30 minutes, 11.2 g (43.5 mmol) of 3-iodoperfluoropropene-1(2) was dropwise added to the mixture, followed by allowing the mixtureto react for 3 hours. The reaction temperature was raised up to 70° C.,at which the reaction was further continued for 1 hour.

The reaction mixture was subjected to gas chromatography to determinethe reaction conversion from the peak area percentages of thechromatogram. The area percentage of the raw material (1) was 53%, andthat of the product (3) was 47%.

The reaction mixture was purified in the same manner as in Example 1 toyield a product (3). IR and ¹H-NMR analyses on the product (3) gavesubstantially the same results as in Example 1 whereby the resultingproduct (3) was identified to be compound No. 1 (R₁: n-C₃H₇).

EXAMPLE 3

Synthesis of Compound No. 1 (R₁: n-C₃H₇)

Compound No. 1(R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 3:

In a nitrogen stream, 13 g (43.5 mmol) of4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (1), 24 g (200 mmol) oftriethylamine, and 84 g of dimethylimidazolidinone (DMI) were put into areactor, followed by heating to 40° C. to prepare a solution. To thesolution was dropwise added 9.2 g (40 mmol) of 3-iodoperfluoropropene-1(2), followed by allowing the mixture to react for 3 hours.

The reaction mixture was subjected to gas chromatography to determinethe reaction conversion from the peak area percentages of thechromatogram. The area percentage of the raw material (1) was 0%, andthat of the product (3) was 100%.

The reaction mixture was purified in the same manner as in Example 1 togive a product (3). IR and ¹H-NMR analyses on the product (3) gavesubstantially the same results as in Example 1 whereby the resultingcompound (3) was identified to be compound No. 1 (R₁: n-C₃H₇).

EXAMPLE 4

Synthesis of Compound No. 1 (R₁: n-C₃H₇)

Compound No. 1(R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 4:

In a nitrogen stream, 12 g (40 mmol) of4-[4-(4-n-propylcyclohexyl)cyclohexyl]phenol (1) and 19 g (40 mmol) ofsodium hydroxide were dissolved in 50 g of dimethylimidazolidinone(DMI). To the solution was added 10.3 g (40 mmol) of3-iodoperfluoropropene-1 (2), followed by allowing the mixture to reactfor 3 hours.

The reaction mixture was subjected to gas chromatography to determinethe reaction conversion from the peak area percentages of thechromatogram. The area percentage of the raw material (1) was 66%, andthat of the product (3) was 34%.

The reaction mixture was purified in the same manner as in Example 1 togive a product (3). IR and ¹H-NMR analyses on the product (3) gavesubstantially the same results as in Example 1 whereby the resultingcompound (3) was identified to be compound No. 1 (R₁: n-C₃H₇).

EXAMPLE 5

Synthesis of Compound No. 2 (R₁: n-C₃H₇)

Compound No. 2 (R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 5:

In dimethylimidazolidinone (DMI) was dissolved 2.35 g (8 mmol) of4-[4-(4-n-propylcyclohexyl)phenyl]phenol (1), and 2.41 g (9.36 mmol,1.17 eq.) of 35 iodoperfluoropropene-1 (2) was added to the solution. Tothe mixture was dropwise added 1.37 g (13.5 mmol, 1.7 eq.) oftriethylamine over 5 minutes while cooling the mixture with water,followed by allowing the mixture to react for 2 hours.

The reaction mixture was neutralized by addition of ethyl acetate andhydrochloric acid, washed with water, dried over magnesium sulfate, andfiltered. The filtrate was concentrated to give a brown solid. Theresulting solid was purified successively by column treatment(toluene/hexane=1/1), kugel-rohr distillation, and crystallization(ethyl acetate/methanol=4/6) to give 1.5 g (yield; 44%) of the titlecompound (3) with 100% purity as white crystals.

The resulting compound (3) was identified to be compound No. 2 (R₁:n-C₃H₇) by infrared (IR) absorption spectrum analysis and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2923 cm⁻¹, 2851 cm⁻¹, 1790 cm⁻¹, 1609 cm⁻¹, 1497 cm⁻¹, 1385 cm⁻¹,1315 cm⁻¹, 1219 cm⁻¹, 1153 cm⁻¹, 1011 cm⁻¹, 826 cm⁻¹, and 791 cm⁻¹

[¹H-NMR] 7.7–7.1 (m, 8H), 2.7–2.3 (m, 1H), 2.1–0.8 (m, 16H)

EXAMPLE 6

Synthesis of Compound No. 3 (R₁: n-C₃H₇)

Compound No. 3 (R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 6:

In a flask purged with argon were put 2.0 g (9.2 mmol) of4-(4-n-propylcyclohexyl)phenol (1), 2.37 g (9.2 mmol, 1.0 eq.) of3-iodoperfluoropropene-1 (2), and 10 g of dimethylimidazolidinone (DMI).While the resulting mixture was stirred under ice cooling, 1.2 g (1.2mmol, 1.3 eq.) of triethylamine (TEA) was added thereto dropwise. Afterthe addition, the mixture was further allowed to react for an addition10 minute period while cooling with ice. The reaction mixture wastreated with water, extracted with hexane, washed with water untilneutrality, dried over magnesium sulfate, and evaporated to remove thesolvent. The residue was purified successively by column treatment(hexane), distillation, and crystallization (methanol) to afford 0.7 g(yield; 24.1%) of the title compound (3) with 99.8% purity as acolorless liquid.

The resulting product (3) was identified to be compound No. 3 (R₁:n-C₃H₇) by infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2859 cm⁻¹, 2924 cm⁻¹, 1851 cm⁻¹, 1790 cm⁻¹, 1670 cm⁻¹, 1593 cm⁻¹,1508 cm⁻¹, 1450 cm⁻¹, 1385 cm⁻¹, 1315 cm⁻¹, 1219 cm⁻¹, 1157 cm⁻¹, and1018 cm⁻¹

[¹H-NMR] 7.3–7.1 (m, 4H), 1.9–0.9 (m, 17H)

EXAMPLE 7

Each of compound Nos. 1 to 3 obtained in Examples 1, 5, and 6 was addedto mother liquid crystal 1 or 2, whose formulation is shown below, in anamount of 10% by mass to prepare a liquid crystal composition.

The resulting liquid crystal compositions were measured for NI point,optical anisotropy (Δn), viscosity (η), and dielectric anisotropy (Δε).Furthermore, extrapolated values of these characteristics were obtained.The results of measurement are shown in Table 1, and the extrapolatedvalues in Table 2. In Tables, NI↑ stands for the NI point in temperaturerise, and NI↓ in temperature drop.

parts by mass Mother Liquid Crystal 1:

21

21

20

10

10

18 Mother Liquid Crystal 2:

34

34

32

TABLE 1 Mother Liquid Crystal Compound No. NI↑ NI↓ Δn η Δε 1 — 52 520.119 23 10.8 2 No. 1 58 57 0.112 22 10.2 (Example 1) 1 — 84.3 83.40.0866 23.3 4.95 1 No. 1 91.8 91.0 0.0872 21.4 4.88 (Example 1) 1 No. 290.1 89.6 0.0939 22.2 4.96 (Example 5) 1 No. 3 73.9 73.0 0.0837 18.54.72 (Example 6)

TABLE 2 Mother Liquid Crystal Compound No. NI↑ NI↓ Δn η Δε 1 No. 1 159159 0.0926 4.14 4.3 (Example 1) 2 No. 1 110 102 0.049 12.6 4.8(Example 1) 1 No. 2 142 145 0.1596 12.5 5.0 (Example 5) 1 No. 3 −19.7−20.7 0.0576 −25.5 2.7 (Example 6)

It is seen from the results in Tables 1 and 2 that the tricyclic ones ofthe perfluoroallyloxy compounds of the present invention have a lowviscosity and a high NI point and that the bicyclic ones are expected toreduce the viscosity of a mother liquid crystal to which they are added.

EXAMPLE 8

Synthesis of Compound No. 4 (R₁: C₂H₅)

Compound No. 4 (R₁: C₂H₅) was synthesized as follows according toreaction scheme 7:

In a flask purged with argon were put 0.57 g (2.71 mmol) of4-(4-ethylcyclohexyl)cyclohexanol (1) and 1.65 g (16.3 mmol, 6.0 eq.) oftriethylamine (TEA), followed by heating under reflux for 1 hour. Themixture was cooled to −20° C., and a solution of 0.70 g (11.6 mmol, 4.3eq.) of 3-iodoperfluoropropene-1 (2) in 1 ml of dimethylimidazolidinone(DMI) was added thereto dropwise over 1 hour, followed by stirring atroom temperature for 14 hours. A 4% hydrochloric acid aqueous solutionand toluene were added to the reaction mixture for liquid—liquidseparation. The organic layer was washed successively with water, asodium hydrogencarbonate aqueous solution, and water until neutralityand dried over magnesium sulfate. The solvent was removed byevaporation. The residue was purified by silica gel columnchromatography (hexane) to give 0.26 g (yield; 27.3%) of the titlecompound (3) with 99.9% purity as a colorless liquid.

The resulting product (3) was identified to be compound No. 4 (R₁: C₂H₅)by infrared absorption spectrum analysis (IR) and ¹H-NMR analysis. Theanalytical results obtained are shown below.

[IR] 2924 cm⁻¹, 2855 cm⁻¹, 2360 cm⁻¹, 2341 cm⁻¹, 1790 cm⁻¹, 1450 cm⁻¹,1381 cm⁻¹, 1315 cm⁻¹, 1223 cm⁻¹, 1173 cm⁻¹, 1026 cm⁻¹, 991 cm⁻¹, 960cm⁻¹, 934 cm⁻¹, 899 cm⁻¹, 795 cm⁻¹, and 664 cm⁻¹

[¹H-NMR] 4.5–4.0 (m, 1H), 2.2–0.4 (m, 24H)

EXAMPLE 9

Synthesis of Compound No. 19 (R₁: n-C₅H₁₁)

Compound No. 19 (R₁: n-C₅H₁₁) was synthesized as follows according toreaction scheme 8:

In a thoroughly dried flask were put 2 g (5.77 mmol) of4-[4-(4-n-pentylcyclohexyl)]cyclohexyl-2-fluorophenol (1), 14 g ofdimethylimidazolidinone (DMI), and 4 g (3.95 mmol) of triethylamine(TEA), followed by stirring under ice cooling. After the mixture wascooled to 3° C., 2.4 g (1.8 eq.) of perfluoroallyl fluorosulfite (2) wasslowly added dropwise. After 15 minutes from completion of the dropwiseaddition, ethyl acetate and water were added to the reaction mixture foroil/water phase separation. The oily phase was dried over magnesiumsulfate and freed of the solvent. Hexane was added to the residue,followed by filtration to remove any insoluble matter. The filtrate waspurified successively by column chromatography and crystallization fromethanol to give 0.6 g (yield; 21.5%) of the title compound (3) with99.9% purity as a colorless solid.

The resulting product (3) was identified to be compound No. 19 (R₁:n-C₅H₁₁) by infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2920 cm⁻¹, 2851 cm⁻¹, 1790 cm⁻¹, 1597 cm⁻¹, 1512 cm⁻¹, 1447 cm⁻¹,1385 cm⁻¹, 1319 cm⁻¹, 1265 cm⁻¹, 1211 cm⁻¹, 1150 cm⁻¹, 1115 cm⁻¹, 1018cm⁻¹, 953 cm⁻¹, 864 cm⁻¹, and 795 cm⁻¹

[¹H-NMR] 7.2–6.8 (m, 3H), 2.6–2.2 (m, 1H), 2.1–0.7 (m, 1H)

EXAMPLE 10

Synthesis of Compound No. 18 (R₁: n-C₅H₁₁)

Compound No. 18 (R₁: n-C₅H₁₁) was synthesized as follows according toreaction scheme 9:

In a flask were put 5 g (13.7 mmol, 1.00 eq.) of4-[4-(4-n-pentylcyclohexyl)cyclohexyl]-1,6-fluorophenol (1), 2.08 g(20.6 mmol, 1.50 eq.) of triethylamine (TEA), and 25 g ofdimethylimidazolidinone (DMI) and dissolved, followed by cooling withice. To the mixture under stirring and ice-cooling was dropwise added3.54 g (13.7 mmol, 1.00 eq.) of 3-iodoperfluoropropene-1 (2). After theaddition, the reaction was continued for an addition 10 minute periodwhile cooling with ice. Hydrochloric acid was added thereto dropwise,and the reaction mixture was phase separated into an aqueous phase andan oily phase. The oily phase was washed with water, dried overmagnesium sulfate, and freed of the solvent. The residue was purifiedsuccessively by silica gel column chromatography (hexane), kugel-rohrdistillation (158–215° C., 017–1.0 mmHg), and crystallization from ethylacetate/methanol (1/1) to give 2.07 g (yield; 30.5%) of the titlecompound (3) with 99.8% purity as a colorless solid.

The resulting product (3) was identified to be compound No. 18 (R₁:n-C₅H₁₁) by infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2924 cm⁻¹, 2853 cm⁻¹, 1790 cm⁻¹, 1630 cm⁻¹, 1601 cm⁻¹, 1514 cm⁻¹,1447 cm⁻¹, 1385 cm⁻¹, 1346 cm⁻¹, 1319 cm⁻¹, 1202 cm⁻¹, 1148 cm⁻¹, 1113cm⁻¹, 1018 cm⁻¹, 959 cm⁻¹, 943 cm⁻¹, 895 cm⁻¹, 851 cm⁻¹, 824 cm⁻¹, 725cm⁻¹, 708 cm⁻¹, 665 cm⁻¹, 646 cm⁻¹, 619 cm⁻¹, and 527 cm⁻¹

[¹H-NMR] 6.9–6.7 (d, 2H), 2.6–0.5 (m, 31H)

EXAMPLE 11

Synthesis of Compound No. 14 (R₁: n-C₅H₁₁)

Compound No. 14 (R₁: n-C₅H₁₁) was synthesized as follows according toreaction scheme 10:

In a flask purged with argon were put 7.98 g (0.03 mol) of5-(4-n-pentylcyclohexyl)-1,3-difluorobenzene (1) and 65 ml oftetrahydrofuran (THF). The mixture was cooled with a methanol/dry icecoolant to −50° C. or lower, and 13.5 ml (0.0351 mol) of a 2.6 mol/lhexane solution of n-butyl lithium was added thereto, followed bystirring for 1 hour. To the reaction mixture kept at −50° C. or lowerwas then added dropwise 3.57 g (0.0343 mol, 1.14 eq.) of dimethoxyboron,followed by stirring for 1 hour. After returning to room temperature, 11ml of a hydrochloric acid aqueous solution (1.2 mol/l) was added theretodropwise, followed by oil/water phase separation. The oily phase waswashed three times with brine, dried over magnesium sulfate, and freedof the solvent to give 6.62 g of4-(4-n-pentylcyclohexyl)-2,6-difluorophenylboronic acid (2).

In a flask were charged 4.56 g (0.021 mol) of4-methoxymethoxy-1-bromobenzene (3), 5.3 g (0.021 mol) of sodiumhydrogencarbonate, 0.147 g (0.021 mol) of Pd[PPh₃]₂Cl₂ complex, 20 ml oftoluene, and 40 ml of water in an argon stream. The mixture was heatedto 75 to 78° C., and a solution of 6.51 g (0.021 mol) of the boronicacid (2) in 20 ml of ethanol was added dropwise thereto, followed byallowing the mixture to react for 1 hour. After cooling, the reactionmixture was separated into an aqueous phase and an oily phase. Afterconfirming the neutrality of the oily phase, the oily phase was driedover magnesium sulfate and freed of the solvent to afford 8.64 g of4-[4-(4-n-pentylcyclohexyl)-2,6-fluorophenyl]-1-methoxymethoxybenzene(4).

In a flask were put 8.45 g of the methoxymethoxy compound (4), 4.38 g ofhydrochloric acid, and 35 ml of tetrahydrofuran (THF), and the mixturewas allowed to react at 70° C. for 2 hours while stirring. Toluene andwater were added to the reaction mixture, followed by liquid—liquidseparation. After confirming neutrality, the organic phase was driedover magnesium sulfate, freed of the solvent, and crystallized fromethyl acetate to give 4.9 g of4-[4-(4-n-pentylcyclohexyl)-2,6-fluorophenyl]phenol (5).

In a flask, 2.87 g (8 mmol) of the phenol compound (5) was dissolved in15 g of dimethylimidazolidinone (DMI). To the solution was added 2.06 g(8 mmol) of 3-iodoperfluoropropene-1 (6), and 1.21 g (8 mmol) oftriethylamine (TEA) was added thereto dropwise at 29 to 33° C. Themixture was allowed to react at 25 to 30° C. for 2 hours. After cooling,the reaction mixture was phase separated by addition of ethyl acetateand water. The oily phase was washed with water until neutrality, driedover magnesium sulfate, and freed of the solvent. The residue waspurified by column chromatography (hexane), kugel-rohr distillation(215° C., 0.35 mmHg), and crystallized from ethyl acetate/methanol (1/3)to give 0.44 g (yield; 10.2%) of the title compound (7) with 99.8%purity as a colorless solid.

The resulting product (7) was identified to be compound No. 14 (R₁:n-C₅H₁₁) by infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2928 cm⁻¹, 2851 cm⁻¹, 1794 cm⁻¹, 1639 cm⁻¹, 1566 cm⁻¹, 1485 cm⁻¹,1431 cm⁻¹, 1385 cm⁻¹, 1315 cm⁻¹, 1218 cm⁻¹, 1188 cm⁻¹, 1161 cm⁻¹, 1057cm⁻¹, 1011 cm⁻¹, 949 cm⁻¹, 845 cm⁻¹, 791 cm⁻¹, 725 cm⁻¹, 656 cm⁻¹, 613cm⁻¹, and 529 cm⁻¹

[¹H-NMR] 7.7–7.1 (m, 4H), 7.0–6.7 (m, 2H), 2.7–2.3 (m, 1H), 2.2–0.8 (m,20H)

EXAMPLE 12

Synthesis of Compound No. 11 (R₁: n-C₃H₇)

Compound No. 11 (R₁: n-C₃H₇) was synthesized as follows according toreaction scheme 11:

In a flask purged with argon were charged 6.2 g (26.1 mmol) of4-(4-propylcyclohexyl)cyclohexylmethanol (1) and 15.8 g (156 mmol, 6.0eq.) of triethylamine (TEA), followed by heating under reflux for 1hour. After cooling to −20° C., 7.9 g (30.8 mmol, 1.18 eq.) of3-iodoperfluoropropene-1 (2) was slowly added thereto dropwise, followedby stirring at room temperature. The reaction mixture was phaseseparated by addition of a hydrochloric acid aqueous solution (9.6 ghydrochloric acid in 24 g water) and 30 ml of toluene. The organic phasewas washed with water, dried over magnesium sulfate, and freed of thesolvent. The residue was subjected to column chromatography (hexane) tofurnish 2.1 g (yield; 21.6%) of the title compound (3) with 99.8% purityas a colorless transparent liquid.

The resulting product (3) was identified to be compound No. 11 (R₁:n-C₃H₇) by infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis. The analytical results obtained are shown below.

[IR] 2920 cm⁻¹, 2851 cm⁻¹, 2623 cm⁻¹, 1790 cm⁻¹, 1450 cm⁻¹, 1412 cm⁻¹,1377 cm⁻¹, 1315 cm⁻¹, 1211 cm⁻¹, 1173 cm⁻¹, 1033 cm⁻¹, 964 cm⁻¹, 941cm⁻¹, 899 cm⁻¹, 806 cm⁻¹, 783 cm⁻¹, 741 cm⁻¹, 664 cm⁻¹, 613 cm⁻¹, and513 cm⁻¹

[¹H-NMR] 3.9–3.7 (d, 2H), 2.2–0.5 (m, 27H)

EXAMPLE 13

In Table 3 below are shown the phase transition temperatures (° C.),optical anisotropy (Δn), and dielectric anisotropy (Δε) of theperfluoroallyloxy compounds according to the present invention. Theoptical anisotropy (Δn) and the dielectric anisotropy (Δε) areextrapolated values obtained from the results of measurement on liquidcrystal compositions prepared by adding 10% by mass of the test compoundto the above-described mother liquid crystal 1.

In Table 3, compound Nos. 1 (R₁: n-C₅H₁₁), 5, 8, 9, and 10 are thoseprepared in accordance with Example 1; compound Nos. 17, 19 (R₁: n-C₃H₇)and 21 are those prepared in accordance with Example 9; and compoundNos. 15, 16, 18 (R₁: n-C₃H₇), and 20 are those prepared in accordancewith Example 10.

TABLE 3 Com- pound Phase No. R₁ Transition Temperatures (° C.) Δn Δε  1n-C₃H₇ Sm→157.3→N→174.2→I 0.0926 4.3 (Exam- ple 1)  1 n-C₅H₁₁Sm→171.7→N→178.7→I 4.3  2 n-C₃H₇ C→45.5→Sm→169.6→N→180.4→I 0.1596 5.0(Exam- ple 5)  3 n-C₃H₇ liquid 0.0576 2.7 (Exam- ple 6)  4 C₂H₅ liquid0.0331 2.97 (Exam- ple 8)  5 n-C₃H₇ C→77→I  8 n-C₄H₉ C→59.6→I  9 n-C₆H₁₃C→33→Sm→53.4→I 10 n-C₈H₁₇ Sm→195→I 11 n-C₃H₇ liquid 0.0141 0.238 (Exam-ple 12) 14 n-C₅H₁₁ C→67.1→Sm→84.9→N→114.1→I 0.126 8.47 (Exam- ple 11) 15n-C₃H₇ C→31.8→N→132.4→I 0.1458 8.00 16 n-C₅H₁₁ liquid 0.0536 5.24 17n-C₅H₁₁ liquid 0.061 4.55 18 n-C₃H₇ Sm→41.2→N→166.6→I 0.1006 7.3 18n-C₅H₁₁ N→165.2→I 0.0916 7.35 (Exam- ple 10) 19 n-C₃H₇ Sm→49.8→N→170.8→I0.1036 5.0 19 n-C₅H₁₁ Sm→44.4→N→170.3→I 0.101 6.0 (Exam- ple 9) 20n-C₃H₇ N→146.2→I 21 n-C₅H₁₁ Sm→101.5→N→168.3→I C: solid phase, Sm:smectic phase, N: nematic phase, I: isotropic phase

The results in Table 3 prove usefulness of the perfluoroallyloxycompounds of the present invention as a liquid crystal material.

EXAMPLE 14

Liquid crystal compositions were prepared using the perfluoroallyloxycompounds of the present invention according to the formulations shownin Table 4 below. The NI point, optical anisotropy (Δn), dielectricanisotropy (Δε), and viscosity (η) of the compositions were measured.The results of measurement are also shown in Table 4.

TABLE 4 Liquid Crystal Composition*¹ Liquid Crystal Compound 1 2 3 4C2-CY-CY-PH-3,4-diF 16 13 11 C3-CY-CY-PH-3,4-diF 17 14 12C5-CY-CY-PH-3,4-diF 16 13 12 C3-CY-PH-PH-3,4-diF 14 5C5-CY-PH-PH-3,4-diF 14 5 C2-CY-C≡C-PH-3,4-diF 2 C5-CY-PH-Cl 7C3-CY-PH-OCH₃ 5 C7-CY-PH-F 4 C5-CY-PH-F 5 C3-CY-PH-OCF₂CF═CF₂ 14 10 5(compound No. 3) C3-CY-PH3F—OCF₂CF═CF₂ 15 (compound No. 17)C5-CY-PH3F—OCF₂CF═CF₂ 13 15 25 (compound No. 17) C3- 16CY-CY-PH3F—OCF₂CF═CF₂ (compound No. 19) C5- 16 CY-CY-PH3F—OCF₂CF═CF₂(compound No. 19) C3-CY-CY-PH3,5- 14 11 diF—OCF₂CF═CF₂ (compound No. 18)C5-CY-CY-PH3,5- 3 18 14 12 diF—OCF₂CF═CF₂ (compound No. 18)C3-CY-PH-PH3,5- 2 12 diF—OCF₂CF═CF₂ (compound No. 15) Results of NIPoint (° C.) 83.0 94.7 88.8 85.2 Measure- Δn (25° C.) 0.0991 0.08700.0852 0.0872 ment Δε (25° C.) 5.1 4.9 4.9 5.4 η (mPa · s) 20 17 14 17CY: 1,4-cyclohexylene, PH: 1,4-phenylene, Cn: straight-chain alkyl grouphaving n carbon atoms and, unless otherwise indicated, bonded to the4-position *¹: in terms of parts by mass

It is seen from Table 4 that use of the perfluoroallyloxy compounds ofthe present invention provides liquid crystal compositions having a lowviscosity, a small refractive index anisotropy (Δn), a large dielectricanisotropy (Δε), and a high NI point (broad nematic phase range).

EXAMPLE 15

Synthesis of Compound No. 22 (R₁: n-C₃H₇) and Phase TransitionTemperatures

Compound no. 22 (R₁: n-C₃H₇) shown below was synthesized in accordancewith Example 9. As a result of infrared absorption spectrum analysis(IR) and ¹H-NMR analysis, the resulting product was identified to becompound No. 22 (R₁: n-C₃H₇). The results of analyses are shown below.

[IR]2924 cm⁻¹, 2851 cm⁻¹, 1794 cm⁻¹, 1593 cm⁻¹, 1566 cm⁻¹, 1497 cm⁻¹,1323 cm⁻¹, 1146 cm⁻¹, 1018 cm⁻¹, 903 cm⁻¹, 829 cm⁻¹, 802 cm⁻¹, and 544cm⁻¹

[¹H-NMR] 7.6–7.2 (m, 7H), 2.8–2.3 (m, 1H), 2.1–0.8 (m, 16H)

The phase transition temperatures (° C.) of the resulting compound No.22 (R₁: n-C₃H₇) were as follows.

-   -   C→46→Sm→129→N→152→I

EXAMPLE 16

Synthesis of Compound No. 23 (R₁: n-C₅H₁₁)

Compound No. 23 (R₁: n-C₅H₁₁) shown below was synthesized in accordancewith Example 9. As a result of infrared absorption spectrum analysis(IR) and ¹HNMR analysis, the resulting product was identified to becompound No. 23 (R₁: n-C₅H₁₁). The results of analyses are shown below.

[IR] 3437 cm⁻¹, 2932 cm⁻¹, 2858 cm⁻¹, 1909 cm⁻¹, 1794 cm⁻¹, 1609 cm⁻¹,1497 cm⁻¹, 1462 cm⁻¹, 1385 cm⁻¹, 1319 cm⁻¹, 1153 cm⁻¹, 1064 cm⁻¹, 1011cm⁻¹, 818 cm⁻¹, 787 cm⁻¹, 733 cm⁻¹, 694 cm⁻¹, 664 cm⁻¹, 629 cm⁻¹, 574cm⁻¹, and 502 cm⁻¹

[¹H-NMR] 7.7–7.1 (m, 8H), 2.8–2.5 (t, 2H), 1.9–0.7 (m, 9H)

EXAMPLE 17

Synthesis of Compound No. 24 (R₁: n-C₃H₇)

Compound No. 24 (R₁: n-C₃H₇) shown below was synthesized in accordancewith Example 9. As a result of infrared absorption spectrum analysis(IR) and ¹HNMR analysis, the resulting product was identified to becompound No. 24 (R₁: n-C₃H₇). The results of analyses are shown below.

[IR] 2963 cm⁻¹, 2936 cm⁻¹, 2874 cm⁻¹, 1790 cm⁻¹, 1628 cm⁻¹, 1601 cm⁻¹,1567 cm⁻¹, 1528 cm⁻¹, 1501 cm⁻¹, 1443 cm⁻¹, 1385 cm⁻¹, 1319 cm⁻¹, 1277cm⁻¹, 1234 cm⁻¹, 1207 cm⁻¹, 1146 cm⁻¹, 1111 cm⁻¹, 1042 cm⁻¹, 1018 cm⁻¹,895 cm⁻¹, 864 cm⁻¹, 837 cm⁻¹, 667 cm⁻¹, and 536 cm⁻¹

[¹H-NMR] 7.5–7.1 (m, 6H), 2.7–2.5 (t, 2H), 1.9–1.5 (m, 2H), 1.1–0.9 (t,3H)

EXAMPLE 18

Synthesis of Compound No. 25 (R₁: n-C₃H₇)

Compound No. 25 (R₁: n-C₃H₇) shown below was synthesized in accordancewith Example 9. As a result of infrared absorption spectrum analysis(IR) and ¹HNMR analysis, the resulting product was identified to becompound No. 25 (R₁: n-C₃H₇). The results of analyses are shown below.

[IR] 2963 cm⁻¹, 2936 cm⁻¹, 2874 cm⁻¹, 1790 cm⁻¹, 1593 cm⁻¹, 1566 cm⁻¹,1497 cm⁻¹, 1466 cm⁻¹, 1431 cm⁻¹, 1385 cm⁻¹, 1319 cm⁻¹, 1265 cm⁻¹, 1200cm⁻¹, 1150 cm⁻¹, 1119 cm⁻¹, 1018 cm⁻¹, 903 cm⁻¹, 876 cm⁻¹, 833 cm⁻¹, 795cm⁻¹, 667 cm⁻¹, and 532 cm⁻¹

[¹H-NMR] 7.6–7.1 (m, 7H), 2.7–2.5 (t, 2H), 1.9–1.5 (m, 2H), 1.1–0.9 (t,3H)

EXAMPLE 19

Synthesis of Compound No. 26 (R₁: n-C₃H₇)

Compound No. 26 (R₁: n-C₃H₇) shown below was synthesized in accordancewith Example. 9. As a result of infrared absorption spectrum analysis(IR) and ¹HNMR analysis, the resulting product was identified to becompound No. 26 (R₁: n-C₃H₇). The results of analyses are shown below.

[IR] 3445 cm⁻¹, 2936 cm⁻¹, 2858 cm⁻¹, 1794 cm⁻¹, 1639 cm⁻¹, 1585 cm⁻¹,1504 cm⁻¹, 1454 cm⁻¹, 1389 cm⁻¹, 1327 cm⁻¹, 1300 cm⁻¹, 1215 cm⁻¹, 1196cm⁻¹, 1150 cm⁻¹, 1107 cm⁻¹, 1050 cm⁻¹, 1018 cm⁻¹, 949 cm⁻¹, 856 cm⁻¹,822 cm⁻¹, 799 cm⁻¹, 710 cm⁻¹, 663 cm⁻¹, 629 cm⁻¹, 606 cm⁻¹, 571 cm⁻¹,544 cm⁻¹, and 525 cm⁻¹

[¹H-NMR] 7.2–6.4 (m, 4H), 2.7–0.5 (m, 17H)

EXAMPLE 20

Synthesis of Compound No. 27 (R₁: n-C₃H₇)

Compound No. 27 (R₁: n-C₃H₇) shown below was synthesized in accordancewith Example 9. As a result of infrared absorption spectrum analysis(IR) and ¹HNMR analysis, the resulting product was identified to becompound No. 27 (R₁: n-C₃H₇). The results of analyses are shown below.

[IR] 3437 cm⁻¹, 2924 cm⁻¹, 2851 cm⁻¹, 1794 cm⁻¹, 1593 cm⁻¹, 1504 cm⁻¹,1389 cm⁻¹, 1319 cm⁻¹, 1261 cm⁻¹, 1207 cm⁻¹, 1150 cm⁻¹, 1099 cm⁻¹, 1022cm⁻¹, 957 cm⁻¹, 872 cm⁻¹, 795 cm⁻¹, and 621 cm⁻¹

[¹H-NMR] 7.3–6.7 (m, 4H), 2.9–2.5 (m, 1H), 2.1–0.5 (m, 21H)

EXAMPLE 21

Synthesis of Compound No. 28

Compound No. 28 shown below was synthesized in accordance with Example9. As a result of infrared absorption spectrum analysis (IR) and ¹H-NMRanalysis, the resulting product was identified to be compound No. 28.The results of analyses are shown below.

[IR] 3433 cm⁻¹, 1794 cm⁻¹, 1497 cm⁻¹, 1389 cm⁻¹, 1319 cm⁻¹, 1227 cm⁻¹,1150 cm⁻¹, 1069 cm⁻¹, 1015 cm⁻¹, and 787 cm⁻¹

[¹H-NMR] 7.7–7.1 (m, 8H)

EXAMPLE 22

In Table 5 below are shown the phase transition temperatures (° C.),optical anisotropy (Δn), and dielectric anisotropy (Δε) of theperfluoroallyloxy compounds according to the present invention. Theoptical anisotropy (Δn) and the dielectric anisotropy (Δε) areextrapolated values obtained from the results of measurement on liquidcrystal compositions prepared by adding 10% by mass of the test compoundto the above-described mother liquid crystal 1.

In Table 5, compound Nos. 15, 18, and 19 are those prepared inaccordance with Example 9.

TABLE 5 Compound No. R₁ Phase Transition Temp. (° C.) Δn Δε 15 C₂H₅C→53.8→N→104.6→I 0.1374 7.1 15 n-C₄H₉ C→32.4→N→127.1→I 0.0924 6.17 15n-C₅H₁₁ Sm→27.9→N→132.6→I 0.1508 8.27 18 n-C₄H₉ C→33.6→N→165.8→I 0.9246.17 19 C₂H₅ Sm→45.0→N→140.8→I 0.094 4.5 23 n-C₅H₁₁ C→98.2→I 0.1174 2.15(Example 16) 24 n-C₃H₇ liquid 0.1024 6.3 (Example 17) 25 n-C₃H₇ C→33.4→I0.11 3.7 (Example 18) 26 n-C₃H₇ C→37.6→N→60.4→I 0.0889 12.6 (Example 19)27 n-C₃H₇ Sm→133.7→N→159.1→I 0.106 1.23 (Example 20) 28 PFA C→65.9→I0.103 0.9 (Example 21) C: solid phase Sm: smectic phase N: nematic phaseI: isotropic phase PFA: —OCF₂CF═CF₂

FORMULATION EXAMPLE

Formulation examples of liquid crystal compositions containing theperfluoroallyloxy compounds of the present invention are shown in Tables6 through 11. In Tables 6 to 11, CY stands for 1,4-cyclohexylene; PH,1,4-phenylene; Pym, 5,2-pyrimidine; and Cn, a straight-chain alkyl grouphaving n carbon atoms and, unless otherwise specified, bonded to the4-position.

The liquid crystal compositions having the formulations of Tables 6 to11 all had a low viscosity, a low refractive index anisotropy (Δn), ahigh dielectric anisotropy (Δε), and a high NI point (i.e., broadnematic phase range).

TABLE 6 Compound Amount Liquid Crystal Compound No. (part by mass)C5-CY-PH-OCF₂CF═CF₂ No. 3  13 C7-CY-PH-F 10 C2-CY-CY-PH-OCF₃ 10C3-CY-CY-PH-OCF₃ 13 C4-CY-CY-PH-OCF₃ 7 C5-CY-CY-PH3F—OCF₂CF═CF₂ No. 1911 C3-CY-CY-CH₂CH₂-PH-3,4-diF 10 C5-CY-CY-CH₂CH₂-PH-3,4-diF 8C3-CY-CY-CH₂CH₂-PH-F 11 C3-CY-PH-PH2F-CY-C3 3 C5-CY-PH-PH2F-CY-C3 2C5-CY-PH-PH2F-CY-C5 2

TABLE 7 Compound Amount Liquid Crystal Compound No. (part by mass)C2-CY-CY-PH3F—OCF₂CF═CF₂ No. 19 13 C3-CY-CY-PH3,4-diF 15 C2-CY-PH-CN 12C3-CY-PH3,5-F—OCF₂CF═CF₂ No. 16 10 CH₃OCH₂-CY-PH-CN 6 C2-PH-COO-PH-CN 6C2-Pym-PH-C2 4 C6-Pym-PH-OCF₂CF═CF₂ No. 9  4 C3-CY-CY-PH-CN 6C2-CY-CY-PH3F—CN 12 C3-CY-CY-PH3F—CN 12

TABLE 8 Compound Amount Liquid Crystal Compound No. (part by mass)C3-CY-PH-CN 10 C3-CY-PH3,5-diF—CN 10 C2-PH-COO-PH3F—CN 2C3-PH-COO-PH3F—CN 3 C5-CY-CY-CH═CH₂ 8 CH₂═CH-CY-CY-PH-CH₃ 14.5C5-CY-CY-PH-OCF₂CF═CF₂ No. 1 14 C3-PH-C≡C-PH-OCF₂CF═CF₂ No. 5 5C2-O-PH-C≡C-PH-CH₃ 5 C3-O-PH-C≡C-PH-CH₃ 5 C2-O-PH-C≡C-PH-F 4CH₂═CH-CY-PH-C≡C-PH-C2 10 CH₃CH═CH-CY-PH-C≡C-PH-C2 9.5

TABLE 9 Compound Amount Liquid Crystal Compound No. (part by mass)C2-CY-CY-PH3,4-diF 8 C3-CY-CY-PH3,4-diF 8 C5-CY-CY-PH3F-OCF₂CF═CF₂ No.19 8 C2-CY-PH-CN 8 C3-CY-PH-CN 2 C3-CY-PH-O-C2 7 C3-CY-PH-OCF₂CF═CF₂ No.3  7 C3-CY-COO-PH-O-C2 6 CH₃OCH₂-CY-CY-C3 5 C2-CY-CY-PH-CH₃ 6C3-CY-CY-PH-C3 14 C3-CY-CY-PH-OCH₃ 4 C3-CY-CY-COO-PH-F 3C5-CY-CY-COO-PH-OCF₂CF═CF₂ * 3 C3-CY-CY-PH-F 4 *Perfluoroallyloxycompound of the present invention

TABLE 10 Amount Compound (part by Liquid Crystal Compound No. mass)C3-CY-CY-C2 10 C3-CY-CY-C5 10 C7-CY-PH-F 5 C3-CY-PH-C4 9C3-CY-PH2,3-diF-OCF₂CF═CF₂ * 11 C5-CY-PH2,3-diF—O-C2 15C3-CY-CY-PH-di2,3-diF—OCF₂CF═CF₂ No. 21 10 C5-CY-CY-PH-2,3-diF—O-C2 12C3-CY-CY-PH2,3-diF—CH₃ 7 C5-CY-CY-PH2,3-diF—CH₃ 11

TABLE 11 Amount Compound (part by Liquid Crystal Compound No. mass)C3-CY3E-CY-C3 5 C3-CY-CY-CF₃ 5 CH₂═CH-CY-CY-C5 8 C3-CY-PH-O—CF₂CF═CF₂No. 3  12 C2-CY-CY-PH3F—O—CF₂CF═CF₂ No. 19 11 C3-CY-CY-PH3F—O—CF₂CF═CF₂No. 19 14 C3-CY-CY-PH3,4-diF 13 C3-CY-CY-PH3,5-diF—O—CF₂CF═CH₂ No. 18 17C4-CY-CY-PH-CF₂H 10 C2-CY-PH-PH-3,4,5-triF 5

INDUSTRIAL APPLICABILITY

The perfluoroallyloxy compound according to the present invention isuseful as a liquid crystal material of a liquid crystal composition foran electro-optical display device of any display mode and any drivesystem.

1. A perfluoroallyloxy compound represented by general formula (I):

wherein R₁ represents R, RO, ROCO or RCOO; R represents an alkyl groupwhich may have an unsaturated bond, a —CH₂— moiety of which may bedisplaced with —O—, —CO— or —COO—, and a part or all of the hydrogenatoms of which may be substituted with a halogen atom or a cyano group;A₁ and A₂ each represent 1,4-phenylene (a —CH═ moiety of which may bedisplaced with —N═, and a part or all of the hydrogen atoms of which maybe substituted with a halogen atom or a cyano group), 1,4-cyclohexylene(a —CH₂— moiety of which may be displaced with —O— or —S—, and a part orall of the hydrogen atoms of which may be substituted with a halogenatom or cyano group), 2,6-naphthylene or 2,6-decahydronaphthylene; Z₁represents a single bond, —COO—, —OCO—, —CH₂CH₂—, —CH═CH—, —(CH₂)₄—,—CH₂O—, —OCH₂—, —(CH₂)₃O—, —O(CH₂)₃—, —CH═CHCH₂O—, —OCH₂CH═CH—, —C≡C—,—CF₂O— or —OCF₂—; B represents a single bond or alkylene group a part ofthe hydrogen atom of which may be substituted with a halogen atom or acyano group; and n represents a number of 1 to 3; when n is 2 or 3, A₁'sand Z₁'s may each be the same or different.
 2. The perfluoroallyloxycompound according to claim 1, wherein R₁ is an unsubstituted alkylgroup or an unsubstituted alkenyl group.
 3. The perfluoroallyloxycompound according to claim 1, wherein R₁ is —O—CF₂CF═CF₂.
 4. Theperfluoroallyloxy compound according to claim 1, wherein A₁ and A₂ areeach an unsubstituted 1,4-phenylene group or an unsubstituted1,4-cyclohexylene group.
 5. The perfluoroallyloxy compound according toclaim 1, wherein at least one of A₁ and A₂ is a 1,4-phenylene groupsubstituted with one or two fluorine atoms.
 6. The perfluoroallyloxycompound according to claim 1, wherein Z₁ is a single bond.
 7. Theperfluoroallyloxy compound according to any one of claim 1, wherein Z₁is —CF₂O—.
 8. A liquid crystal composition containing theperfluoroallyloxy compound according to claim
 1. 9. An electro-opticaldisplay device having the liquid crystal composition according to claim8 sealed in a liquid crystal cell thereof.